Process for preparing polycarbonate having reduced carbonate byproduct content

ABSTRACT

A process for preparing polycarbonate wherein a chain terminator is added to the reaction mixture after substantial reaction of a carbonate precursor, a coupling catalyst is added to the reaction mixture after substantial reaction of the chain terminator, and base is added to the reaction mixture after reaction mixture after substantial reaction of the chain terminator in an amount sufficient to give a negative chloroformate test.

FIELD OF THE INVENTION

This invention relates to a prices for reducing the carbonate byproductcontent and polydispersity in polycarbonate, and to the polycarbonateproduced thereby.

BACKGROUND OF THE INVENTION

This invention relates to polycarbonate, and the production thereof,where a chain terminator has been utilized in the manufacturing process,and to articles fabricated from such polycarbonate.

It is known to produce polycarbonate by the reaction of a dihydroxycompound, particularly a diphenol, with a carbonic acid derivative suchas phosgene. A chain terminator is often added to the reaction mixturefor the purpose of regulating the molecular weight of the polycarbonateproduct. When used, a chain terminator is typically included in themonomer mix which is initially charged to the reaction vessel, and thedihydroxy compound and chain terminator are consequently both present inthe reaction mixture when it is contacted with the carbonic acidderivative.

In such a method of producing polycarbonate, molecules of varyingdegrees of polymerization are obtained. The chain terminator is usefulfor the purpose of attempting to confine a large percentage of themolecules to a preselected molecular weight range. However, even when aterminator is used according to the practice in the art as describedabove, not all molecules conform to the preselected weight range, andfrequently some molecules of extremely low molecular weight (carbonatebyproducts) are nevertheless produced.

Carbonate byproducts, being the smallest of the molecules resulting fromthe production of polycarbonate, have the lowest respective boilingpoints and are therefore the most likely to exist in vapor phase. Thepresence of carbonate byproducts in vapor phase becomes a considerationwhen polycarbonate is, for example, being extruded, molded, or heatedfor any other purpose. Accordingly, it would be desirable to prevent orlimit the formation of carbonate byproducts in polycarbonate, and obtaina polycarbonate product wherein the greatest possible percentage of themolecules fall within the preselected molecular weight range which it isthe purpose of a chain terminator to achieve.

For the purpose of reducing the formation of carbonate byproducts inpolycarbonate, U.S. Pat. No. 4,939,230 (which is incorporated herein inits entirety) discloses the general procedure of withholding addition ofa chain terminator to a polycarbonate reaction mixture until reaction ofthe dihydroxy compound and carbonic acid derivative has proceeded tocompletion. However, additional process steps concerning the timing ofadmixture of base or a coupling catalyst with the reaction mixture havebeen found to be a valuable refinement of that general procedure.

SUMMARY OF THE INVENTION

This invention involves a process for preparing polycarbonate comprising(a) forming a carbonate oligomer by contacting a carbonate precursorwith a solution containing a dihydroxy compound, water, a solventcapable of dissolving a carbonate precursor, and a base: (b) admixing achain terminator with said solution after said carbonate precursor hasbeen substantially completely reacted with said solution: (c) forming apolycarbonate by admixing a coupling catalyst with said solution aftersaid chain terminator has been substantially completely reacted withsaid solution, (d) recovering polycarbonate from said solution.

In another aspect, this invention involves a process for preparingpolycarbonate comprising (a) forming a carbonate oligomer by contactinga carbonate precursor with a solution containing a dihydroxy compound,water, a solvent capable of dissolving a carbonate precursor, and abase; (b) admixing a chain terminator with said solution after saidcarbonate precursor has been substantially completely reacted with saidsolution: (c) forming a polycarbonate by admixing with said solution,after said chain terminator has been substantially completely reactedtherewith, sufficient base to impart to said solution a negativechloroformate test: (d) recovering a polycarbonate product from saidsolution.

In yet another aspect, this invention involves a process for preparingpolycarbonate comprising (a) forming a carbonate oligomer by contactinga carbonate precursor with a solution containing a dihydroxy compound,water, and a base: (b) admixing a solvent capable of dissolving acarbonate oligomer with said solution after said carbonate precursor hasbeen substantially completely reacted with said solution: (c) admixing achain terminator with said solution after dissolution of said carbonateoligomer: (d) forming a polycarbonate by admixing a coupling catalystwith said solution after said chain terminator has been substantiallycompletely reacted with said solution: (e) recovering polycarbonate fromsaid solution.

The process of this invention is useful for producing a polycarbonatewhich is characterized by desirably low levels of carbonate byproducts.The presence of such carbonate byproducts often causes partial pluggingof mold vents and thus uneven flow of molten extrudate into all parts ofa mold cavity, leaving imperfections in finished polycarbonate articlesmade, for example, by injection molding. Also by the process of thisinvention, a polycarbonate having a desirably low polydispersity isobtained.

The polycarbonate produced by the process of this invention may beemployed, for example, as a membrane, film, fiber, extruded sheet,multi-layer laminate or molded or shaped article of virtually anyvariety. Such molded or shaped articles are particularly adapted for usein the automotive and electronics industries, for example as informationstorage media such as a compact disc. When softened by the applicationof heat, the polycarbonate of this invention may be readily formed ormolded using conventional techniques such as vacuum- or thermo-forming,calendering, or compression, injection, extrusion or blow moldingtechniques, alone or in combination, for fabrication into any of theitems mentioned above. A polycarbonate can also be compounded with oneor more other organic or inorganic substances.

DETAILED DESCRIPTION OF THE INVENTION

In the process of this invention--the process for making thepolycarbonate of this invention--polycarbonate can be prepared by thereaction of a dihydroxy compound and a carbonate precursor such as acarbonic acid derivative, a haloformate or a carbonate ester. Thesecomponents are usually reacted by means of the phase boundary process inwhich the dihydroxy compound is dissolved and deprotonated in an aqueousalkaline solution and the carbonate precursor is dissolved in an organicsolvent. The aqueous alkaline solution can be formed from a base whichmay be selected from those including the alkali metal and alkaline earthmetal phosphates, bicarbonates, oxides and hydroxides. A preferred basefor such purpose is a caustic soda such as NaOH.

These components may be reacted in a mixture which is typically preparedinitially from the dihydroxy compound, water and a non-reactive,immiscible organic solvent selected from among those in which thecarbonate precursor and polycarbonate product are soluble.Representative solvents include chlorinated hydrocarbons such asmethylene chloride, 1,2-dichloroethane, tetrachloroethane,chlorobenzene, and chloroform, to which tetrahydrofuran, dioxane,nitrobenzene, dimethyl sulfoxide, xylene, cresol or anisole may beadded, if desired. Caustic soda or other base is added to the reactionmixture to adjust its pH to a level at which the dianion of thedihydroxy compound is formed. A reducing agent such as sodium sulfite orsodium dithionite can also be advantageously added to the reactionmixture. Optionally, the solvent may be added later so that a carbonateprecursor is added in the absence of a solvent.

A carbonate precursor is contacted with an agitated mixture of theaqueous alkaline solution of the dihydroxy compound, and, for suchpurpose, the carbonate precursor can be bubbled into the reactionmixture in the form of a gas, or can be dissolved and introduced insolution form. The mixture is agitated in a manner which is sufficientto disperse or suspend droplets of the solvent containing the carbonateprecursor in the aqueous alkaline solution. Reaction at the interface ofthe organic and aqueous phases created by such agitation yields themonomeric bisester of the dihydroxy compound [hereinafter referred to asthe "bis(carbonate precursor)ester of the dihydroxy compound"]. Forexample, if the carbonate precursor is a carbonyl halide such asphosgene, the products of this initial phase of the process arepredominantly monomers in dichloroformate form accompanied by lesseramounts of oligomers which are either mono- or dichloroformates orbisphenolate ions.

The molecular weight of the polycarbonate can be controlled by additionto the reaction mixture of a chain terminator which may be selected frommonofunctional substances such as phenols, alcohols, amines, imides,carbonic acid chlorides, sulfonic acid chlorides, metallic sulfites,trialkyl- or triarylsilanols, monohalosilanes, aniline orphenylchlorocarbonates. Of these, phenol and derivatives thereof such asp-(t-butyl)phenol, and 4-(1,1,3,3-tetramethyl-butyl)-phenol("4-tert-octyl phenol"), allyl phenol and cumyl phenol are the mostpreferred. Addition of a chain terminator is made to the reactionmixture after a carbonate precursor is completely reacted with adihydroxy compound.

The intermediate carbonate oligomers formed by the process as describedabove dissolve in the organic solvent as they form, and they can becondensed to a higher molecular weight, final polycarbonate product bycontact with a coupling catalyst of which the following arerepresentative: a tertiary amine such as triethyl amine or an activatedpyridine, for example a 2- or 4-substituted pyridine such as4-dimethylaminopyridine; a hindered secondary amine such as diisopropylamine; a cyclic aza compound such as 2,2,6,6-tetramethyl piperidine or1,2-dimethylimidazole: an amidine or aminoamidine compound such as1-methyl-2-phenyliminopyrrolidine; an isourea compound such asN,N-dibutyl-N'-phenyl-o-methylisourea; an iminoether or iminocarboxylatecompound such as 1-aza-2-methoxy-1-cycloheptene ort-butyl-cyclohexyliminoacetate; or a phosphonium, sulfonium, arsonium orquaternary ammonium compound.

Upon completion of polymerization, the organic and aqueous phases areseparated to allow purification of, and recovery of the polycarbonateproduct from, the organic phase. The organic phase is washed as neededin a centrifuge with water, dilute base and/or dilute acid until free ofunreacted monomer, residual process chemicals and/or other electrolytes.Recovery of the polycarbonate product from the organic phase can beeffected by spray drying, steam devolatilization, directdevolatilization in a vented extruder, or precipitation by use of ananti-solvent such as toluene, cyclohexane, heptane, methanol, hexanol,or methyl ethyl ketone.

The reaction can be run at a temperature between 0° C.-100° C., althoughusually not in excess of the boiling point of the solvent used.Frequently, the reaction is run at a temperature of about 0° C. to about45° C.

Representative examples of dihydroxy compounds suitable for use in thepreparation of a polycarbonate include one or more of the variouslybridged aromatic diols represented generally by the formula ##STR1##wherein:

(I) Z is (A) a divalent radical, of which all or different portions canbe (i) linear, branched, cyclic or bicyclic, (ii) aliphatic or aromatic,and/or (iii) unsaturated, said divalent radical being composed of 1-35carbon atoms together with up to five oxygen, nitrogen, sulfur,phosphorus and/or halogen (such as fluorine, chlorine and/or bromine)atoms; or (B) S, S₂, SO, SO₂, O or CO; or (C) a single bond: and

(II) each X is independently hydrogen, a halo radical (such as fluroine,chlorine and/or bromine), or a C₁ -C₁₂ linear or cyclic alkyl, alkoxy,aryl or aryloxy radical, such as methyl, ethyl, isopropyl, cyclopentyl,cyclohexyl, methoxy, ethoxy, benzyl, tolyl, xylyl, phenoxy and/orxylynoxy.

For example the bridge represented by Z in the above formula can be acarbon atom to which is bonded one or more groups such as CH₃, C₂ H₅, C₃H₇, n-C₃ H₇, i-C₃ H₇, cyclohexyl, bicyclo[2.2.1]heptyl, benzyl, CF₂,CF₃, CCl₃, CF₂ Cl, CN, (CH₂)₂ COOCH₃, or PO(OCH₃)₂.

The polycarbonate of the present invention can also be prepared fromdihydroxy benzenes such as pyrocatechol, resorcinol and hydroquinone,and from dihydroxy naphthalenes and anthracenes, and their halo-, alkyl-and aryl-substituted derivatives.

Representative dihydroxy compounds of particular interest in thisinvention include the following:

bis(4-hydroxyphenyl)sulphone,

bis(3-hydroxyphenyl)sulphone,

bis(2-hydroxyphenyl)sulphone,

bis(4-hydroxyphenyl)ketone,

bis(4-hydroxyphenyl)methane,

1,1-bis(4-hydroxyphenyl)propane,

1,1-bis(4-hydroxyphenyl)butane,

1,1-bis(4-hydroxyphenyl)heptane,

1,1-bis(4-hydroxyphenyl)cyclopentane,

1,1-bis(4-hydroxyphenyl)cyclohexane,

2,2-bis(4-hydroxyphenyl)propane,

bis(hydroxyphenyl)fluorene,

1-phenyl,1,1-bis(4-hydroxyphenyl)ethane, ("Bisphenol-AP)

2,2-bis(3,5-dibromo,4-hydroxyphenyl) propane ("Tetrabromo Bisphenol-A"or "TBBA"),

2,2-bis(3,5-dichloro,4-hydroxyphenyl) propane ("TetrachloroBisphenol-A"), and

2,2-bis(3,5-dimethyl,4-hydroxyphenyl) propane ("TetramethylBisphenol-A");

and the like. Among these, 2,2-bis(4-hydroxyphenyl)propane("Bisphenol-A") is especially preferred.

Known processes for preparing polycarbonate are described generally inSchnell, U.S. Pat. No. 3,028,365; Campbell, U.S. Pat. No. 4,384,108;Glass, U.S. Pat. No. 4,529,791; and Grigo, U.S. Pat. No. 4,677,162, eachbeing incorporated herein in its entirety.

The preferred process of this invention is that in which an aromaticpolycarbonate is prepared. An aromatic polycarbonate is defined hereinwith reference to the oxygen atoms, of the dihydroxy compounds presentin the copolycarbonate chain, which are bonded to a carbonyl carbon. Inan aromatic polycarbonate, all such oxygen atoms are bridged by adihydroxy compound residue some part of which is an aromatic ring.

In a preferred embodiment of the process of this invention, the reactionis conducted independently in a series of individual reaction vesselswherein at least a portion of the reaction mixture prepared in a firstreaction vessel in a first step is transferred to a second reactionvessel wherein another step is performed thereon, and so on throughoutthe process whereby other later steps can, if desired, be performed inother vessels.

Carbonate byproducts typically result when a chain terminator is chargedto a monomer mix before a carbonic acid derivative has been fullyreacted therein with a dihydroxy compound. Any terminator anion capableof attacking an hydroxy or carbonic acid ester end group on a completedpolymer chain is also capable of undesirably either (1) attackingunreacted molecules of the initial charge of the carbonic acidderivative, or (2) displacing end group before a chain has anopportunity to grow to the desired length. The practice of adding chainterminator to a reaction mixture prior to complete reaction of thecarbonic acid derivative consequently allows the formation of carbonatebyproducts by the occurrence of both of the aforesaid results.

Different carbonate byproducts can result during the manufacture ofpolycarbonate, two of those more commonly encountered beingmonocarbonate and dicarbonate. For example, when a dihydroxy compound,an unreacted carbonic acid derivative and a chain terminator aresimultaneously present in the monomer mix, a side reaction directlybetween two equivalents of chain terminator and the carbonic acidderivative can yield monocarbonate. Monocarbonate contains one carbonylcarbon bonded to the residue of two equivalents of terminator, butcontains no dihydroxy compound residue. Correspondingly, dicarbonateresults when two equivalents of carbonic acid derivative have beencoupled by a dihydroxy compound but then have each been stopped fromfurther such chain growth by terminator. Dicarbonate contains oneterminator residue and a carbonyl carbon and linked to a second carbonylcarbon/terminator unit by a dihydroxy compound residue.

When a dihydroxy compound, an unreacted carbonic acid derivative and,for example, a phenolic chain terminator are simultaneously present inthe monomer mix, carbonate byproducts which can result may be generallyrepresented by a formula such as ##STR2## where R is the ring portion ofthe phenolic terminator, and X is the bridging portion of the dihydroxycompound; a=0 gives monocarbonate, and a=1 gives dicarbonate. Certainvalues of a greater than 1 can also represent carbonate byproducts.

Because of the desire to prevent, inhibit or reduce the formation ofcarbonate byproducts, the process of this invention involves thepractice of withholding addition of chain terminator to a polycarbonatereaction mixture until reaction of the carbonic acid derivative with thedihydroxy compound has proceeded to completion. This reaction occursvery quickly, and can be regarded as substantially complete as soon asthe carbonic acid derivative has been thoroughly admixed with the othercomponents of the reaction mixture. When carbonic acid derivative ispresent in the reaction mixture in the preferred amount of about 1.15 toabout 1.5 moles, and more preferably about 1.2 to about 1.3 moles, ofcarbonic acid derivative per mole of dihydroxy compound, the reactioncan be regarded as substantially instantaneous.

If desired, a test can be run to determine the amount of unreacteddihydroxy compound remaining in the aqueous phase of the reactionmixture. If sufficient dihydroxy compound has been consumed, accordingto the relative amounts of dihydroxy compound and carbonate precursorpresent in the monomer mix, the completion of reaction of all, orsubstantially all, of the carbonic acid derivative can be determined.For example, if about 1.15 to about 1.5 moles of carbonic acidderivative per mole of dihydroxy compound is present in the reactionmixture, a dihydroxy compound content in the aqueous phase of less than2 weight percent, and preferably less than 1,000 weight parts permillion, indicates substantial completion of the reaction of thecarbonic acid derivative.

When a terminator is not present in the reaction mixture beforecompletion of reaction of the carbonic acid derivative, premature attackby the terminator on the unreacted portion of a carbonic acid derivativeis not possible, thereby preventing or reducing the formation theformation of carbonate by products.

As important as it is to follow this practice to reduce carbonatebyproduct content, it is also desirable to follow additional processsteps which (i) reduce the pre-coupling molecular weight of theintermediate carbonate oligomers, (ii) reduce the polydispersity of thefinal, polycarbonate product, as well as (iii) enhance the likelihoodthat the formation of carbonate byproducts, particularly dicarbonate,will be reduced.

To help reduce the molecular weight of the intermediate carbonateoligomers before they are condensed into a final, high molecular weightpolycarbonate product, base is added to the monomer mix beforecompletion of reaction of the carbonic acid derivative, and preferablybefore the carbonic acid derivative is itself added to the mixture, inan amount per mole of dihydroxy compound given by 2+4Y(Z-1) whereY=about 0 to about 0.5, and preferably about 0.2 to about 0.4, andZ=moles of carbonic acid derivative per mole of dihydroxy compound.Running the reaction in a highly agitated state and with excess water,for example in excess of 8 moles of water per mole of dihydroxycompound, also has the effect of reducing the molecular weight of theintermediate carbonate oligomers.

To help reduce the polydispersity of the final, high molecular weightpolycarbonate product, a chain terminator is added to, thoroughlyadmixed with and preferably substantially completely reacted with thereaction mixture, before a coupling catalyst is added thereto. Ifdesired, an analytical test such as liquid chromatography can be run todetermine the amount of unreacted terminator remaining in the reactionmixture. When such a test shows substantial absence of the terminatorfrom the reaction mixture, or shows a constant level thereof has beenreached, substantially complete reaction of the terminator in thereaction mixture has been reached. Polydispersity control is likewiseaided if further base is also added to the reaction mixture after thechain terminator has been thoroughly admixed and reacted therewith. Baseshould be added at such point in the reaction in an amount sufficient toimpart to the reaction mixture a negative chloroformate test. Forexample, one known such test involves the use of4(4-nitrobenzyl)pyridine, which turns orange in the presence ofchloroformates.

The value of these process steps may be noted not only in a desirablylow amount of carbonate byproducts in the polycarbonate producedthereby, but also in a low pre-coupling molecular weight for theintermediate carbonate oligomers, and a low polydispersity (weightaverage molecular weight divided by number average molecular weight) inthe final polycarbonate product. A polycarbonate made by the process ofthis invention is characterized by (i) a monocarbonate content of lessthan 100, and preferably less than 50, parts by weight per million partsof polycarbonate ("ppm"), (ii) less than 0.8 percent, and preferablyless than 0.6 percent, of dicarbonate, based on the weight of thepolycarbonate, and (iii) a polydispersity of less than 3.0 andpreferably less than 2.5. Before coupling, a polycarbonate oligomer madeby the process of this invention is characterized by a weight averagemolecular weight of about 1,500 to about 8,000 and preferably about1,500 to about 4,000.

A branched rather than linear polycarbonate molecule can be obtained byadding to the reaction mixture a tri- or polyfunctional monomer such asa tri- or tetrafunctional phenol or carboxylic acid (or derivativethereof such as an acyl halide or anhydride), a bisphenol containingcarboxylic acid side groups, or a nitrogen-containing compound such ascyanuric chloride, or compounds containing a mixture of such groups.

Instead of a polycarbonate, a carbonate copolymer (a copolycarbonate)can be prepared by incorporating into the reaction mixture two or moredifferent dihydroxy compounds, which can be charged to the reactionmixture either simultaneously or sequentially. If the dihydroxycompounds are added sequentially or added together but have differentreactivities toward the carbonate precursor, a segmented or blockcopolycarbonate will typically result. Different dihydroxy compoundswith the same reactivity typically yield a random copolycarbonate whenreacted together. Alternatively, if oligocarbonates are formedseparately from one or more different dihydroxy compounds, theoligocarbonates can then be coupled in a condensation reaction to yielda segmented or block copolycarbonate. When a dicarboxylic acid (orderivative) or a hydroxycarboxylic acid is used in the reaction mixture,or to form an oligomeric prepolymer, instead of one of the differentdihydroxy compounds, a poly(ester/carbonate) is obtained instead of apolycarbonate.

A copolycarbonate can also be prepared by reaction of a dihydroxycompound, and optionally one or more other dihydroxy compounds, with acarbonate precursor and, for example, the following; ahydroxy-terminated poly(phenylene oxide) or poly(methyl methacrylate), aphosphonyl dichloride, or an aromatic ester of a phosphonic acid, or byreaction in the presence of a chlorine- or amino-terminatedpolysiloxane. Siloxane/carbonate block copolymers are discussed ingreater detail in Paul, U.S. Pat. No. 4,596,970 andpoly(ester/carbonate)s are discussed in greater detail in Swart, U.S.Pat. No. 4,105,533, each being incorporated herein in its entirety.

Polycarbonate blends can be prepared from a polycarbonate by admixingtwo or more different polycarbonates; or by admixing a polycarbonatewith one or more other kinds of carbonate polymers, such as analternating or block copolycarbonate, a homopolycarbonate (being thatwhich is prepared from only one dihydroxy compound), or apoly(ester/carbonate); and/or with one or more other kinds of polymersor copolymers, such as polyethylene, polyester, polyacetal, polyamide,polysulfone, poly(phenylene oxide), acrylonitrile/butadiene/styrenecopolymer, methacrylate/butadiene/styrene copolymer, and/orstyrene/maleic anhydride copolymer.

The process of this invention can further involve compounding with apolycarbonate conventional thermoplastic polymer additives whichinclude, but are not limited to, fillers, thermal stabilizers, dyes,flame retarding agents, reinforcing agents, softeners, mold-releaseagents, seed-forming agents, pigments, plasticizers, antistatic agents,UV absorbers, lubricants, compatibilizers, and the like, in conventionalamounts generally not exceeding 25 percent, and preferably not exceeding5 percent, by weight of the total composition.

ILLUSTRATIVE EMBODIMENTS

To illustrate the practice of this invention, examples of preferredembodiments are set forth below. It is not intended, however, that theseexamples (Examples 1-2) should in any manner restrict the scope of thisinvention. Some of the particularly desirable features of this inventionmay be seen by contrasting the characteristics of Examples 1-2 withthose of controlled processes (Controls A and B) which do not possessthe features of, and are not therefore embodiments of, this invention.

Control A

550 grams of Bisphenol-A are added to 2,700 grams of water, 570 grams of34% NaOH and 2,250 grams of methylene chloride in a 2 gallonphosgenation reactor. The mixture is stirred to dissolve theBisphenol-A, and phosgene addition is started at a rate of 3grams/minute. After 150 grams of phosgene has been added, 200 grams of34% NaOH is added and phosgenation is continued. A total of 300 grams ofphosgene is added. After phosgenation is complete, 17.6 grams ofp-tertiarybutyl phenol ("PTBP") is added. After thorough admixture ofthe PTBP with the other reaction components, the phosgenated oligomersare transferred to a 3 gallon coupling reactor containing 3,625 grams ofmethylene chloride, 100 grams of 34% NaOH and 2.8 grams of triethylamine("TEA"). The mixture is stirred to the end of the polycarbonate-formingreaction as indicated by a negative chloroformate test.

Control B

The same process as described in Control A is performed except that thePTBP is present in the coupling reactor when the phosgenated oligomersare added thereto.

EXAMPLE 1

700 grams of Bisphenol-A are added to 3,300 grams of water, 780 grams of34% NaOH and 2,700 grams of methylene chloride in a 2 gallonphosgenation reactor. The mixture is stirred to dissolve theBisphenol-A, and phosgene addition is started at a rate of 4grams/minute. A total of 372 grams of phosgene is added. Afterphosgenation is complete, 19 grams of PTBP is added. After thoroughadmixture of the PTBP with the other reaction components, thephosgenated oligomers are transferred to a 3 gallon coupling reactorcontaining 4,680 grams of methylene chloride, 650 grams of 34% NaOH and3.6 grams TEA. The mixture is stirred to the end of thepolycarbonate-forming reaction as indicated by a negative chloroformatetest.

EXAMPLE 2

68.5 grams of Bisphenol-A are added to 360 grams of water and 88 gramsof 34% NaOH in a 1 liter phosgenation reactor. The mixture is stirred todissolve the Bisphenol-A, and phosgene addition is started at a rate of1 gram/minute. A total of 49 grams of phosgene is added. Afterphosgenation is complete, 570 grams of methylene chloride are added todissolve the white oligomer precipitate. After thorough stirring, 2.2grams of PTBP are added, followed by 66 grams of 34% NaOH. Afterthorough admixture of the PTBP with the other reaction components, 0.38grams of TEA is added. The mixture is stirred to the end of thepolycarbonate-forming reaction as indicated by a negative chloroformatetest.

Each of the polycarbonates prepared by the processes of Controls A and Band Examples 1-2 is analyzed to determine mono- and dicarbonate content,weight average and number average molecular weight, and polydispersity.The oligomers produced by each process are also tested for molecularweight before coupling.

Weight and number average molecular weight determinations are performedby gel permeation chromatography ("GPC") using a Bisphenol-Apolycarbonate standard.

Measurement of the quantity of mono- and dicarbonate in thepolycarbonate samples made in each process was accomplished byhigh-performance reverse-phase liquid chromatography. The samples wereanalyzed on a Hewlett Packard 1090 chromatograph, using a 15 cm×4 mmI.D. column, packed with Spherisorb ODS II three micron packing.Tetrahydrofuran/H₂ O was used as the carrier solvent. UV absorbtion at264±5 nm was determined for each oligomer as it eluted from the column.Absorbtion peaks were compared to those generated by standardizationsamples containing carefully measured amounts of mono- and dicarbonate.A monocarbonate content of less than 50 ppm is not detectable by thismethod of measurement, and as monocarbonate is not detected in any ofthese samples, each is deemed to have less than 50 ppm monocarbonate.

Moles of NaOH per mole of dihydroxy compound ("DHC") added beforecompletion of phosgenation, dicarbonate content, molecular weights andpolydispersity are reported in Table I for the polycarbonates preparedby each of the processes of Controls A and B and Examples 1-2.

                                      TABLE I                                     __________________________________________________________________________    Results of Tests on Samples from Controls A-B and Examples 1-2                Polycarbonate     Pre-Coupling                                                                           Coupled Molecular                                                                            Dicarbonate                         Produced by the                                                                        Moles of NaOH                                                                          Weight Average                                                                         Weight    Poly-                                                                              Content,                            Process of                                                                             per mole of DHC                                                                        Molecular Weight                                                                       Weight                                                                             Number                                                                             dispersity                                                                         weight percent                      __________________________________________________________________________    Control A                                                                              2.7      9,619    20,981                                                                             7,743                                                                              2.7  1.1                                 Control B                                                                              2.7      --       29,979                                                                             7,913                                                                              3.8  0.2                                 Example 1                                                                              2.2      4,050    24,860                                                                             9,438                                                                              2.6   0.30                               Example 2                                                                               2.46    1,514    21,186                                                                             9,144                                                                              2.3  0.1                                 __________________________________________________________________________

The results of the foregoing tests demonstrate the value of followingthe additional steps of this invention when seeking to reduce carbonatebyproduct formation by withholding chain terminator addition until afterphosgenation. In the process of Control A, more base was added to thereaction mixture before completion of phosgenation per mole of dihydroxycompound than given by 2+4Y(Z-1) where Y=about 0 to about 0.5 andZ=moles of carbonic acid derivative per mole of dihydroxy compound. Thisresulted in a polycarbonate product having an undesirably highdicarbonate content. In the process of Control B, more base was added tothe reaction mixture before completion of phosgenation per mole ofdihydroxy compound than given by the above equation, and the chainterminator was not added and thoroughly admixed with the other reactioncomponents before the coupling catalyst was added. This resulted in apolycarbonate product having an undesirably high polydispersity.

In the respective processes of Examples 1-2, which illustrate thisinvention, the base added to the reaction mixture before completion ofphosgenation meets the above equation, and the chain terminator wasadded and thoroughly admixed with the other reaction components beforethe coupling catalyst was added. This resulted, respectively, inpolycarbonate products having both a desirably low polydispersity anddicarbonate content.

What is claimed is:
 1. A process for preparing polycarbonatecomprising(a) forming a carbonate oligomer by contacting a carbonylhalide with a dihydroxy compound dianion in a reaction mixturecontaining water, a solvent capable of dissolving a carbonyl halide, anda base in an amount per mole of dihydroxy compound given by 2+4Y(Z-1)moles where Y=about 0 to about 0.5 and Z=about 1.15 to about 1.5, (b)admixing a chain terminator with said reaction mixture after saidcarbonyl halide has been substantially completely reacted with saiddianion of said dihydroxy compound in said reaction mixture, (c) forminga polycarbonate by admixing a carbonate oligomer condensation catalystwith said reaction mixture after said chain terminator has beensubstantially completely reacted with said reaction mixture, (d)recovering a polycarbonate produce from said reaction mixture.
 2. Theprocess of claim 1 further comprising admixing with said reactionmixture, after said chain terminator has been substantially completelyreacted with said reaction mixture, sufficient base to impart to saidreaction mixture a negative chloroformate test.
 3. The process of claim1 wherein said polycarbonate preparation process is conducted in aseries of individual reaction vessels wherein a carbonyl halide iscontacted with a dihydroxy compound dianion in the reaction mixture instep (a) in a first reaction vessel, and at least one of steps (b) or(c) is performed on said reaction mixture in a second reaction vessel.4. The process of claim 1 further comprising admixing a dicarboxylicacid, or derivative thereof, or a hydroxycarboxylic acid with saidreaction mixture in step (a).
 5. The process of claim 1 wherein saiddihydroxy compound is one or more of the members of the group consistingof Bisphenol-A, Tetrabromobisphenol-A, Tegtramethylbisphenol-A,Bisphenyl-A-P, and Bis(hydroxyphenyl)fluorene, and the chain terminatoris phenol or a substituted derivative thereof.
 6. The process of claim 1wherein Z=about 1.2 to about 1.3.
 7. The process of claim 1 wherein theamount of water in step (a) is in excess of 8 moles per mole ofdihydroxy compound.
 8. The process of claim 7 further comprisingadmixing with said reaction mixture, after said chain terminator hasbeen substantially completely reacted with said reaction mixture,sufficient base to impart to said reaction mixture a negativechloroformate test.
 9. The process of claim 1 wherein the carbonateoligomer has a weight average molecular weight of about 1,500 to 8,000.10. The process of claim 9 further comprising admixing with saidreaction mixture, after said chain terminator has been substantiallycompletely reacted with said reaction mixture, sufficient base to impartto said reaction mixture a negative chloroformate test.